Photoinitiated Reactions of Haloperfluorocarbons with Gold(I) Organometallic Complexes: Perfluoroalkyl Gold(I) and Gold(III) Complexes |
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Authors: | Alejandro Portugués Inmaculada López-García Javier Jiménez-Bernad Dr Delia Bautista Dr Juan Gil-Rubio |
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Institution: | 1. Departamento de Química Inorgánica, Facultad de Química, Universidad de Murcia, Campus de Espinardo, 30100 Murcia, Spain;2. ACTI., Universidad de Murcia, Campus de Espinardo, 30100 Murcia, Spain |
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Abstract: | The study of perfluoroalkyl metal complexes is key to understand and improve metal-promoted perfluoroalkylation reactions. Herein, we report the synthesis of the first gold complexes with primary or secondary perfluoroalkyl ligands by photoinitiated reactions between AuI organometallic complexes and iodoperfluoroalkanes. Complexes of the types LAuRF (L=PPh3 or N,N-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; RF=n-C4F9, n-C6F13, i-C3F7, c-C6F11) and Au(RF)(Ar)I(PPh3)] (Ar=2,4,6-trimethylphenyl) have been isolated and characterized. Alkynes RFC≡CR were formed by reaction of Ph3PAuC≡CR (R=Ph, nHex) with IRF (RF=n-C4F9, i-C3F7). According to the evidences obtained, this transformation undergoes through a photoinitiated radical mechanism. AuIII complexes Au(n-C4F9)(X)(Y)L] (X=Y=Cl, Br, I, Me; X=Me, Y=I) have been prepared or in situ generated, and their thermal or photochemical decomposition reactions have been studied. |
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Keywords: | fluorinated ligands gold oxidative addition photochemical reactions radicals |
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